Process for continuous dyeing polyester fiber material with anthraquinone dyestuff

ABSTRACT

IN WHICH X, Y and n have the meaning given in the description below and are subsequently subjected to a heat treatment. There are obtained without originating waste waters dyeings which are characterised by excellent fastness properties.   Process for the continuous dyeing of synthetic fibre materials from organic solvents wherein the fibre materials are impregnated with dye liquors containing anthraquinone dyestuffs of the formula

United States Patent 91 Hederich et al.

[ Aug. 28, 1973 Manfred Groll, all of Cologne, Germany [73] Assignee:Bayer Aktlengesellschaft,

Leverkusen, Germany [22] Filed: Jan. 28, I971 [2]] Appl. No.: 110,591

[30] Foreign Application Priority Data Feb. 4, 1970 Germany P 20 05012.8

[52] US. Cl 8/39, 8/25, 8/93, 8/174, 260/373 [51] Int. Cl D06p 1/20 [58]Field of Search 8/25, 174, 94, 39; 260/373 [56] References Cited UNITEDSTATES PATENTS 3,557,l55 1/1971 Yamada et al 260/373 3,510,243 5/1970Seuret et al 8/174 X 3,505,362 4/1970 Hederich et al. 260/373 OTHERPUBLICATIONS WAS White Amer. Dyestuff Reporter, July 31, I967,

pages 18-24 TP890 AS I2.

Straley et al., Def. Pub. of Serial No. 677,016 filed Oct. 23, 1967,published in 856OG670 on Nov. 19, 1968, Defensive Publication No.T856,03l.

Primary Examiner-Mayer Weinblatt Assistant Examiner-T. .1. Herbert, Jr.Attorney-Plumley & Tyner 5 7 ABSTRACT Process for the continuous dyeingof synthetic fibre materials from organic solvents wherein the fibrematerials are impregnated with dye liquors containing anthraquinonedyestuffs of the formula in which X, Y and n have the meaning given inthe description below and are subsequently subjected to a heattreatment. There are obtained without originating waste waters dyeingswhich are characterised by excellent fastness properties.

8 Claims, No Drawings PROCESS FOR CONTINUOUS DYEING POLYESTER FIBERMATERIAL WITH ANTHRAQUINONE DYESTUFF The invention relates to a processfor the continuous dyeing of synthetic fibre materials from organicsolvents; more particularly it concerns a process for the continuousdyeing of synthetic fibre materials from organic solvents wherein thefibre materials are impregnated with dye liquors containinganthraquinone dyestuffs of the formula in which X stands for one of thegroups OR, COOR, O-COR'or --OCO,R where R denotes an alkyl, cycloalkyl,aralkyl or aryl radical; for the group OSO,R where R denotes an alkyl,cycloalkyl, aralkyl; aryl or dialkylamino radical; or for anaryloxy-sulphonyl group; Y denotes a halogen atom, an alkyl or alkoxygroup;

and n is a number from to 3,

and that they are subsequently subjected to a heat treatment.

For X OR there may be mentioned, for example: as alkoxy radicals: C -C-alkoxy radicals, such as the methoxy, ethoxy, propoxy, isopropoxy,n-butoxy, isobutoxy, n-amyloxy, n-hexyloxy, n-heptyloxy, noctyloxy,isooctyloxy, n-nonyloxy, n-decyloxy, ndodecyloxy, n-tetradecyloxy,n-hexadecyloxy and noctadecyloxy radicals; as cycloalkoxy radicals: thecyclohexyloxy and methylcyclohexyloxy radicals; as aralkoxy radicals:the benzyloxy radical and the methylbenzyloxy radical; as aryloxyradicals: the phenoxy and methyl-phenoxy radicals.

For X COOR there may be mentioned, for example: as alkoxycarbonylradicals: primarily C,--C ,-alkoxycarbonyl radicals, such as themethoxycarbonyl, ethoxycarbonyl, propoxy-carbonyl, isopropoxycarbonyl,butoxycarbonyl, amyloxycarbonyl, hexyloxycarbonyl,2-ethylhexyloxycarbonyland decyloxycarbonyl radical; ascycloalkoxy-carbonyl radicals: the cyclohexyloxycarbonyl andmethyl-cyclohexyloxy-carbonyl radical; as aralkoxy-carbonyl radicals:the benzyloxycarbonyl and methyl-benzyloxy-carbonyl radical; asaryloxy-carbonyl radicals: the phenoxycarbonyl,

methyl-phenoxy-carbonyl, ethylphenoxycarbonyl, propylphenoxycarbonyl,chlorophenoxycarbonyl, methoxyphenoxycarbonyl, isopropoxyphenoxycarbonyland chloro-methyl-phenoxycarbonyl radical.

For X O-C0-R, there may be mentioned, for

example:

as alkyl-carbonyloxy radicals; primarily C,C alkanoyloxy radicals, suchas the acetyloxy, propionyloxy, isopropionyloxy, n-butyryloxy,tert.-butyryloxy, npentanoyloxy, nhexanoyloxy, 2-ethyl-hexanoyloxy,nheptanoyloxy, n-octanoyloxy, n-decanoyloxy, nundecanoyloxy,ndodecanoyloxy, n-tetradecanoyloxy and n-hexadecanoyloxy radical; ascycloalkyl-carbonyloxy radicals: the cyclohexylcarbonyloxy andmethyl-cyclohexyl-carbonyloxy radical; as aralkyl-carbonyloxy radicals:the benzylcarbonyloxy and methylbenzyl-carbonyloxy radical; asaryl-carbonyloxy radicals: the benzoyloxy, methylbenzoyloxy,ethylbenzoyloxy and naphthoyloxy radical.

For X OCO R there may be mentioned, for example:

as alkoxy-carbonyloxy radicals: primarily C C alkoxy-carbonyl radicals,such as the methoxycarbonyloxy, ethoxy-carbonyloxy, propoxycarbonyloxy,butoxycarbonyloxy, amyloxycarbonyloxy and hexyloxycarbonyloxy radical;as cycloalkoxy-carbonyloxy radicals: the cyclohexyloxy-carbonyloxy andmethylcyclohexyloxy-carbonyl radical; as aralkoxy-carbonyloxy radicals:the benzyloxycarbonyloxy and methylbenzyloxy-carbonyloxy radical.

For X OSO,R there may be mentioned, for example: as alkane-sulphonyloxyradicals: primarily C,C alkane-sulphonyloxy radicals, such as themethanesulphonyloxy, ethane-sulphonyloxy, propanesulphonyloxy,isopropanesulphonyloxy, n-butanesulphonyloxy, isobutane-sulphonyloxy,see-butanesulphonyloxy, n-pentane-sulphonyloxy, isopentanesulphonyloxy,n-hexane-sulphonyloxy, iso-hexanesulphonyloxy, n-octane-sulphonyloxy,n-decanesulphonyloxy, n-dodecane-sulphonyloxy,n-tetradecane-sulphonyloxy and n-hexadecane-sulphonyloxy radical;furthermore, substituted alkane-sulphonyloxy radicals, such as theB-propoxy-ethane-sulphonyloxy radical;

as cycloalkane-sulphonyloxy radicals: the cyclohexanesulphonyloxy andmethyl-cyclohexane-sulphonyloxy radicals;

as aralkyl-sulphonyloxy radicals: the benzylsulphonyloxy andmethylbenzyl-sulphonyloxy radical; as aryl-sulphonyloxy radicals: thebenzenesulphonyloxy, methylbenzene-sulphonyloxy,ethylbenzene-sulphonyloxy, propylbenzene-sulphonyloxy,chloro-benzene-sulphonyloxy and methoxybenzenesulphonyloxy radical;

as dialkylamino-sulphonyloxy radicals: C,C -dialkylarnino-sulphonyloxyradicals, such as the N,N- dimethylamino-sulphonyloxy,N,N-diethylaminosulphonyloxy and N,N-dipropylamino-sulphonyloxyradicals;

For X there may be mentioned the following aryloxysulphonyl radicals:the phenoxy-sulphonyl, isopropylphenoxy-sulphonyl,tert.butyl-phenoxy-sulphonyl, amyl-phenoxy-sulphonyl,n-octyl-phenoxy-sulphonyl, iso-nonyl-phenoxy-sulphonyl,di-iso-propyl-phenoxysulphonyl, triethylphenoxy-sulphonyl,chloro-methylphenoxy-sulphonyl and iso-propoxy-phenoxysulphonylradicals.

For Y there may be mentioned: as halogen atom: primarily the chlorineatom;

as alkyl group, C,-C, --alkyl groups, such as the methyl, ethyl, propyl,isopropyl, n-butyl, tert.-butyl, pentyl, isopentyl, hexyl, heptyl,n-octyl, isooctyl, nonyl and dodecyl groups;

as alkoxy group; C,--C,,-alkoxy groups, such as the methoxy, ethoxy,propoxy, isopropoxy, butoxy and pentoxy groups.

In the process according to the invention, those anthraquinone dyestuffsof the formula (I) are preferably used, in which X stands for OR, OCOR,OSO R or an aryloxy-sulphonyl group; among these, those dyestuffs of theformula (I) have proved particularly satisfactory, in which X stands fora group ---OSO,R or OCOR and n 0.

The dyestuffs which are to be used according to the invention for thedyeing from organic solvents are obtained by known methods, for example,by reacting lamino-4-hydroxy-anthraquinones carrying in the 2- positionan exchangeable substituent, such as a chlorine or bromine atom, asulphonic acid group or an aryloxy radical, with suitable phenols in thepresence of inorganic or organic bases, optionally in inert organicsolvents; furthermore by treating suitable 1-amino-4-hydroxy-2-hydroxyaryloxy-anthraquinones with the usual alkylating oracylating agents in the presence of inorganic or organic bases in inertorganic solvents; or also by reacting the sulphochlorides of suitable 1-amino-4-hydroxy-2-aryloxy-anthraquinones with appropriate hydroxyarylcompounds in an aqueous-alka line medium optionally with the addition ofinert organic solvents.

Organic solvents suitable for the process according to the invention arethose solvents which are not miscible with water and the boiling pointof which lies between 40 and 150C, for example, aromatic hydrocarbons,such as toluene or xylene; aliphatic halogenated hydrocarbons, primarilychlorinated hydrocarbons, such as methylene chloride, chloroform, carbontetrachloride,

1,1-dichloroethane, 1,2-dichloroethane, 1,1,2- trichloroethane, l l ,l,Z-tetrachloroethane, l ,l ,2,2- tetrachloroethane, pentachloroethane,lchloropropane, l ,2-dichloro-propane, 1 ,l ,ltrichloropropane,l-chlorobutane, 2-chlorobutane,

1,4-dichlorobutane, 1-chloro-2-methylpropane or2-chloro-2-methylpropane; as well as aliphatic fluorochlorinatedhydro-carbons, such as perfluoro-nhexane, 1,2,2trifluoro-trichloroethaneand 1,1,1- trifluoro-pentachloropropane; and aromatic chlorinated andfluorinated hydrocarbons, such as chlorobenzene, fiuorobenzene,chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene and 1,1,1- trichloroethane haveproved particularly satisfactory. Mixtures of these solvents can also beused.

The synthetic fibre materials to be dyed according to the process of theinvention are primarily fibre materi-v als of polyesters, e.g.polyethylene terephthalates or polyesters of1,4-bis-(hydroxymethyl)-cyclohexane and terephthalic acid; cellulosetriacetate; synthetic polyamides, such as poly-e-caprolactam,polyhexamethylene-diamine adipate or poly-waminoundecanic acid;polyurethanes; polyolefines; or polycarbonates. The fibre materials maybe prsent in the form of fabrics or knitted fabrics.

For dyeing, the dyestuffs to be used according to the invention aredissolved in the water-immiscible organic solvents, or they are added tothe latter in the form of solutions in solvents of unlimited solubilitywith these solvents, such as alcohols, dimethyl formamide, dimethylacetamide, dimethyl sulphoxide or sulpholane; the synthetic fibrematerials are impregnated with the resultant clear dyestuff solutionswhich may contain soluble non-ionic auxiliaries to improve the levelnessof the dyeings, e.g. the known interface-active ethoxylation andpropoxylation products of fatty alcohols, alkylphenols, fatty acidamides and fatty acids. The dyestufis are subsequently fixed on thefibre materials by a heat treatment. The heat treatment may consist in abrief treatment with dry heat at 120 230C with an intermediate dryingpossibly preceding the treatment with dry heat, or in treating the fibrematerials in overheated solvent vapour at 150C. Small amounts ofnon-fixed dyestuff particles can be washed out by a brief treatment withthe cold organic solvent. It should be noted that mixtures of thedyestuffs to be used ac cording to the invention sometimes give a betterdyestuff yield than the individual dyestuffs and that they may be morereadily soluble in the organic solvent.

With the aid of the process according to the invention it is possible,when dyeing from organic solvents, to achieve on synthetic fibrematerials dyeings which are characterised by a high dyestuff yield, verygood build-up and outstanding fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light. Another advantageof the dyestuffs to be used according to the invention consists in theirhigh solubility in organic solvents, especially in tetrachloroethylene,trichloroethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane,which enables the dyeing to be carried out without the use ofsolubilizers.

The parts given in the following Examples are parts by weight.

EXAMPLE 1 A fabric of polyethylene terephthalate fibres is impregnatedat room temperature with a clear red solution containing 10 partslamino-2-(3'-n-hexane-sulphonyloxyphenoxy )-4-hydroxy-anthraquinone in990 parts tetrachloroethylene.

After squeezing to a weight increase of 60 percent, the fabric is driedat 80C for 1 minute. The dyestuff is subsequently fixed by heating thefabric to 190 220C for 45 seconds. The small amount of non-fixeddyestuff is subsequently washed out by a short treatment of 20 secondsin cold tetrachloro-ethylene. After drying, there is obtained a clearred dyeing which is characterised by its high dyestuff yield, very goodbuild-up and outstanding fastness properties, especially by very goodfastness to thermofixing, washing, rubbing and light.

Clear red dyeings of the same good quality were obtained in an analogousway from (a) cellulose triacetate, (b) synthetic polyamides orpolyurethanes and (c) polypropylene fibres, but the thermosolisation wascarried out for (a) at 200 220C, for (b) at 170 220C and for (c) at C.

Equally satisfactory dyeings were also obtained when the 990 partstetrachloroethylene were replaced with the same amount of one of thefollowing solvents: methylene chloride, choroform, carbon tetrachloride,dichloroethane, trichloroethane, trichloroethylene, tetrachloroethane,dichloropropane, 1,1 ,1- trichloropropane, chlorobutane, dichlorobutane,perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane and 1 ,1,l-trifluoro-pentachloropropane.

The dyestuff used above had been prepared as follows:

5 parts 1-amino-2-(m-hydroxy-phenoxy)-4-hydroxyanthraquinone weredissolved in 60 parts pyridine. The solution was mixed first with fiveparts triethylamine, then within 30 minutes at room temperature with 6parts n-hexane-sulphochloride. After further stirring for one hour atroom temperature, the resultant dyestuff was separated by the additionof 80 parts methanol and 20 parts of ice, it was subsequently filteredoff with suction and washed with methanol and water. Yield: 6.5 parts ofthe above compound; melting point after recrystallisation from pyridine:91 92C.

EXAMPLE 2 A knitted fabric of polyhexamethylene-diamine adipatefilaments is impregnated at room temperature with a clear red solutioncontaining parts l-amino-2-[o-( n-decanoyloxy)-phenoxy]-4-hydroxy-anthraquinone and 7 parts nonylphenol heptaethylene glycol etherin 983 parts tetrachloroethylene. After squeezing to a weight increaseof 60 percent, the knitted fabric is dried at 80C for one minute. Thedyestuff is subsequently fixed by heating the knitted fabric to 192C for45 seconds. Small amounts of non-fixed dyestuff are then washed out by ashort treatment of about seconds in cold tetrachloro-ethylene. Afterdrying, there is obtained a clear red dyeing which is characterised byits high dyestuff yield, very good build-up and outstanding fastnessproperties, especially by very good fastness to thermofixing, washing,rubbing and light.

An equally satisfactory dyeing was obtained when the 983 partstetrachloroethylene were replaced with the same amount of toluene,xylene, chlorobenzene or dichlorobenzene.

The dyestuff used above had been prepared as follows:

6 parts l-amino-2-(o-hydroxy-phenoxy)-4-hydroxyanthraquinone dissolvedin 60 parts pyridine were mixed with 9 parts n-decanic acid anhydride.The reaction mixture was subsequently heated at 60C for one hour,diluted with 100 parts methanol and subsequently kept for several hoursin an ice-bath. The precipitated dyestuff was filtered off with suction,washed with methanol and water and dried. Yield: 7.7 parts of the abovecompound; melting point after recrystallisation from pyridine: 77 78C.

EXAMPLE 3 A fabric of polypropylene fibres is impregnated at roomtemperature with a clear red solution containing 10 partsl-amino-2-(oisopropoxy-phenoxy)-4- hydroxy-anthraquinone and 7 partsnonylphenol heptaethylene glycol ether in 983 parts tetrachloroethylene.After squeezing to a weight increase of 60 percent, the fabric is driedat 80C for one minute. The dyestuff is subsequently fixed by heating thefabric to 140C for 30 seconds. Any non-fixed dyestuff particles can bewashed out by a short treatment in the cold solvent. A red dyeing isobtained, which is characterised by its high dyestuff yield, very goodbuild-up and good fastness properties, especially by good fastness tothermofixing, washing, rubbing and light.

The dyestuff used above had been prepared as follows:

parts 2-hydroxy-1-is0propoxy-benzene and l 1 parts potassium carbonatewere heated at C for two hours. After the addition of 40 partsN-methylpyrrolidone and 15 parts l-amino-2-bromo-4-hydroxyanthraquinone,the reaction mixture was heated at C for two hours, then acidified withglacial acetic acid and subsequently distilled with steam. 18 Parts ofthe above compound were obtained.

EXAMPLE 4 A fabric of poly-l,4-cyclohexane-dimethylene terephthalate isimpregnated at room temperature with a clear red solution containing 10parts l-amino-2-[p-(2-ethylhexyloxy-carbonyl)-phenoxy]-4-hydroxy-anthraquinone and 7 parts nonylphenol heptaethyleneglycol ether in 983 parts tetrachloroethylene. After squeezing to aweight increase of 60 percent, the fabric is dried at 80C for 1 minute.The dyestuff is subsequently fixed by heating the fabric to 220C for 45seconds. The small amount of non-fixed dyestuff is then removed by ashort treatment of 20 seconds in cold tetrachloroethylene. After drying,there is obtained a clear red dyeing which is characterised by its highdyestuff yield, very good build-up and outstanding fastness properties,especially by very good fastness to therrnofixing, washing, rubbing andlight.

The dyestufl' used above had been prepared as follows: 8 parts anhydrouspotassium carbonate were dissolved in 80 parts 4-hydroxy-benzoicacid-(2'-ethyhexyl)- ester at l30-l40C. After the introduction of 10parts l-amino-2-bromo-4-hydroxy-anthraquinone, the reaction mixture washeated at 150C for four hours and subsequently cooled to about 60C. Theresultant dyestuff was precipitated by the addition of 120 partsmethanol and 50 parts of water, subsequently filtered off with suction,and washed with methanol and water. Yield: 12.4 parts of the abovecompound; melting point after recrystallisation from pyridine: 103 104C.

EXAMPLE 5 A fabric of anionic-modified polyethylene terephthalate fibres(Dacron 64 is impregnated at room temperature with a clear red solutioncontaining 5 parts 1-amino-2-[p-(p-tosyloxy)-phenoxy]-4-hydroxy-anthraquinone,

5 parts l-amino-2-[p-(o-tosyloxy)-phenoxy]-4- hydroxy-anthraquinone and7 parts nonylphenol heptaethylene glycol ether in 983 partstetrachloroethylene. After squeezing to a weight increase of 60 percent,the fabric is dried at 80C for one minute. The dyestuff is subsequentlyfixed by heating the fabric to 190 220C for 45 seconds. The small amountof non-fixed dyestuff is then washed out by a short rinsing with coldtetrachloroethylene. After drying, there is obtained a clear red dyeingwhich is characterised by a high dyestuff yield, very good build-up andoutstanding fastness properties, especially by very good .fastness tothermofixing, washing, rubbing and light.

The dyestuffs used above had been prepared as described in Example 1but, instead of l-amino-Z-(mhydroxy-phenoxy)-4-hydroxy-anthraquinone,the same amount of 1-amino-2-(p-hydroxyphenoxy)-4-hydroxyanthraquinonewas reacted with the equivalent amount of p-tosyl chloride respectivelyo-tosyl chloride. After recrystallisation from pyridine the resultant1-amino-2- [p-(p-tosyloxy)-phenoxy]-4-hydroxy-anthraquinone melted at174 175C, the corresponding l-amino-Z-[p-(o-tosyloxy)-phenoxyl-4-hydroxy-anthraquinone at 131 132C.

EXAMPLE 6 A fabric of polyethylene terephthalate fibres is impregnatedat room temperature with a clear red solution containing 10 parts1-amino-2-[p-(n-octyloxy)-phenoxy]-4- hydroxy-anthraquinone in 990 parts1,1 1 -trichloroethane.

After squeezing to a weight increase of 60 percent, the dyestuff isfixed by treating the fabric for 45 seconds with overheated1,1,1-trichloroethane vapour at 140C. The small amount of non-fixeddyestufi is subsequently washed out by briefly rinsing in cold 1,1,1-trichloroethane. After drying, there is obtained a clear red dyeingwhich is characterised by its high dyestuff yield, very good build-upand outstanding fastness properties.

An equally satisfactory red dyeing was obtained by the same method ofoperation on a fabric of polycarbonate fibres.

The dyestuff used above had been prepared as follows:

parts 1-amino-2-(p-hydroxy-phenoxy) 4-hydroxyanthraquinone were heatedtogether with 3.5 parts of anhydrous sodium carbonate and 7 partsp-toluenesulphonic acid n-octyl ester in 50 parts of anhydrousnitrobenzene at 200C for 45 minutes. After cooling to 60C, the resultantdyestuff was precipitated by adding 80 parts methanol to the reactionmixture. After filtering off with suction and washing with methanol andwater, there were obtained 5.3 parts and by steam distillation of thenitrobenzene filtrate a further 2.2 parts of the above compound; meltingpoint after recrystallisation from pyridine: 116 117C.

EXAMPLE 7 A knitted fabric of anionic-modified polyarnide fibres (NylonT 844 is impregnated at room temperature with a clear red solutioncontaining 10 parts 1-amino-2-( o-methoxy-phenoxy )-4-hydroxy-anthraquinone and 7 parts nonylphenol heptaethylene glycol etherin 983 parts tetrachloroethylene.

After squeezing to a weight increase of 60 percent, the knitted fabricis dried at 80C for one minute. The dyestuff is subsequently fixed byheating the knitted fabric to 192C for 45 seconds. Small amounts ofnon-fixed dyestuff are then washed out by a short treatment of aboutseconds in cold tetrachloroethylene. After drying, there is obtained ared dyeing which is characterised by a high dyestufi yield, very goodbuild-up and good fastness properties, especially by good fastness tothennofixing, washing, rubbing and light.

The dyestufi' used above had been prepared as follows:

35 parts of anhydrous potassium carbonate were dissolved in 250 partsZ-methoxy-phenol by heating at C for 2 hours. After the introduction of50 parts 1-amino-2-chloro-4-hydroxy-anthraquinone, the reaction mixturewas heated at C for five hours and subsequently cooled to about 60C. Theresultant dyestuff was precipitated by the addition of 200 partsmethanol, subsequently filtered off with suction and washed withmethanol and water. 49.1 Parts of the above compound were obtained;melting oint after recrystallisation from pyridine: 181C.

EXAMPLE 8 A fabric of cellulose triacetate fibres is impregnated at roomtemperature with a clear red solution containmg 10 partsl-amino-2-[m-(n-decanoyloxy)-phenoxy]- 4-hydroxy-anthraquinone and 7parts nonylphenol heptaethylene glycol ether in 983 partstetrachloroethylene.

After squeezing to a weight increase of 60 percent, the fabric is driedat 80C for 1 minute. The dyestuff is subsequently fixed by heating thefabric at 215C for one minute. A clear red dyeing is obtained, which ischaracterised by a high dyestuff yield, very good texture andoutstanding fastness properties, especially by very good fastness tothermofixing, washing, rubbing and light.

The dyestuff used above was obtained in analogy with the dyestuffdescribed in Example 2 but the 1-amino-2-(o-hydroxy-phenoxy)-4-hydroxyanthraquinone there used wasreplaced with the equivalent amount of l-amino-2-(m-hydroxy-phenoxy)-4-hydroxy-anthraquinone. After recrystallisation from pyridine, theresultant dyestuff melted at 68 70C.

Clear red dyeings with equally satisfacotry fastness properties werealso obtained on fabrics of polyester, triacetate, polyamide,polyurethane, polycarbonate and polyolefine fibres, when the dyestuffsdescribed in Examples 1 8 were replaced with the dyestuffs listed in thefollowing Table:

Example Dyestuff 9 1-amino-2-[0-(methane-sulphonyloxyl-phenoxyl-4-hydroxy-anthraquinone l-amino-2-[o-(n-decane-sulphonyloxy)-phenoxy]-4-hydroxy-anthraquinone l-amino-2-[m-(n-butane-sulphonyloxy)-phenoxyl-4-hydroxy-anthraquinone 4-hydroxy-anthraquinone ExampleDyestuff 2l 1-amino-2-[m-(n-pentanoyloxy)-phenoxy]-4-hydroxy-anthraquinone 22 l-amino-2-[p-(n-decanoyloxy)-phenoxy]-4-hydroxy-anthraquinone 23 l-amino-2-[0-(n-butoxycarbonyl)-phenoxy]-4-hydroxy-anthraquinone 24 l-amino-2-[m-(n-octyloxycarbonyD-phenoxy]-4-hydroxy-anthraquinone 25 1-amino-2-[p-(n-hexyloxycarbonyD-phenoxy]-4-hydroxy-anthraquinone 261-amino-2-[p-(iso-pentyloxycarbonyl)- phenoxy]-4-hydroxy-anthraquinone27 l-amino-2-[o-(n-butane-sulphonyloxy)-phenoxy]-4-hydroxy-anthraquinone 28l-amino-2-[0-ethoxy-phenoxy1-4-hydroxyanthraquinone 29l-amino-2-[o-propoxy-phenoxy]-4-hydroxyanthraquinone 3Ol-amino-2-[m-(n-butoxy)-phenoxy]-4-hydroxyanthraquinone 31l-amino-2-[m-(n-octyloxy)-phenoxy]-4-hydroxyanthraquinone 32l-amino-2-[p-(isooctyloxy)-phenoxy] 4-hydroxyanthraquinone 33l-amino-2-[p-(n-dodecyloxy)-phenoxy]-4- anthraquinone 34l-amino-2-[m-(n-heptyloxy)-phenoxy]-4- hydroxy-anthraquinone 35l-amin0-2-[o-isoamyloxy-phenoxy]-4- hydroxy-anthraquinone 36l-amino-2-[p-(p'-methyl-benzoyloxy)- phenoxy]-4-hydroxy-anthraquinone 371-amino-2-[m-(m-trifluoromethylbenzoyloxy)-phenoxy]-4-hydroxy-anthraquinone 38l-amino-2-[0-(p-tert.butyl-benzoyloxy)- phenoxy]4-hydroxy-anthraquinone39 l-amino-2[p-(ethoxycarbonyloxy)-phenoxyl- 4-hydroxy-anthraquinone 401-amino-2-[m-(propoxycarbonyloxy)-phenoxy1- 4-hydroxy-anthraquinone 411-amino-2-[0-(phenoxycarbonyloxy)- phenoxy]-4-hydroxy-anthraquinone 42l-amino-2-[o-chloro-p-(isoamyloxycarbonyD-phenoxy]-4-hydroxy-anthraquinone 43l-amin0-2-[m-benzyloxy-phenoxy]-4-hydroxyanthraquinone 44l-amino-2-[m-cyclohexyloxy-phenoxy]-4- hydroxy-anthraquinone 451-amino-2-[o-rnethoxy-m-methyl-phenoxy]- 4-hydroxy-anthraquinone 46l-amino-2-[o-methoxy-p-methyl-phenoxy1- 4-hydroxy-anthraquinone 47l-amino-2-[0-m-dimethoxy-phenoxy1- 4-hydroxy-anthraquinone 481-amino-2-[0-ethoxy-p-methyl-phenoxy1- 4-hydroxy-anthraquinone 49l:amino-Z-[b-methoxy-m-(n-pentane-sulphonyloxy)-phenoxy]4-hydroxy-anthraquinone 50l-amino-2-[m-methyl-p-(n-hexanesulphonyloxy)-phenoxy]-4-hydroxyanthraquinone5 1 l-amino-2-[p-butyl-m-(methane-sulphonyloxy)-phenoxy]-4-hydroxy-anthraquinone 52l-amino-2-[m-methyl-p-(n-butoxycarbonyl)-phenoxy]-4-hydroxy-anthraquinone 531-amino-2-[p-(p-dodecylphenoxysulphonyl)-phenoxy]-4-hydr0xy-anthraquinone 10 v Example Dyestuff 54l-amino-2-[p-(p-terr.butylphenoxysulphonyhphenoxyl-4-hydroxy-anthraquinone55 l-amino-2-[p-(p'-isooctylphenoxysulphonyl)-phenoxy]-4-hydroxy-anthraquinone 561-amino-2[p-(p-isopropylphenoxysulphonyl)-phenoxy1-4-hydroxy-anthraquinone 57l-amin0-2-[pr(0-sec.butylphenoxysulphonyl)-phenoxy]-4-hydroxy-anthraquinone 581-amino-2-[p-(o-isopropylphenoxysulphonyD-phenoxy]-4-hydroxy-anthraquinone 59 l-amino-2-[p-tert.butyl-oand-m-(p-tert.butylphenoxysulphonyl)phenoxy]-4-hydroxyanthraquinone,mixture 60 l.-amin0-2-[p-terLbutyl-oandm-(p-isooctylphenoxy-sulphonyl)-phenoxy]-4-hydroxyanthraquinone, mixture61 1-amino-2-[p-isooctyl-oand-m-(p'-tert.butylphenoxy-sulphonyl)-phenoxy]-4-hydroxyanthraquinone,mixture 62 l-amino-2-[p-isooctyl-oand-m-(p-isooctylphenoxy-sulphonyl)-phenoxy]-4-hydroxyanthraquinone,mixture 63 l-amino-2-[0,p-dimethyl-m-(p-tert.butylphenoxy-sulphonyl)-phenoxy]-4-hydroxyanthraquinone64 l-amino-2-[o-chloro-m-methyl-p-(pisooctylphenoxy-sulphonyl)-phenoxy]-4-hydroxy-anthraquinone.

EXAMPLE 65 A fabric of polyethylene terephthalate fibres is impregnatedat room temperature with a clear red solution containing 10 partsl-amino-2[p-(p-nonylphenoxysulphonyl)- phenoxy]-4-hydroxy-anthraquinoneand 7 parts nonylphenol heptaethylene glycol ether in 983 partstetrachloroethylene.

After squeezing to a weight increase of 60 percent, the fabric is driedat C for one minute. The dyestuff is subsequently fixed by heating thefabric to 190 220C for 45 seconds. The small amount of non-fixeddyestuff is then washed out by a short rinsing with coldtetrachloroethylene. After drying, there is obtained a clear red dyeingwhich is characterised by its high dyestuff yield, very good build-upand very good fastness properties, especially by very good fastness tothermofixing, washing, rubbing and light.

The dyestuff used above had been prepared as follows:

10 parts l-amino-2-phenoxy-4-hydroxyanthraquinone were introduced at 05C into a mixture of 50 parts chlorosulphonic acid and 5 parts thionylchloride. The reaction mixture was slowly heated to 50C, kept at thesame temperature for 1 k hours, cooled and poured on to ice. Theprecipitated sulphochloride was suction filtered and washed withice-water until neutral. The moist sulphochloride was subsequentlyintroduced at room temperature into a mixture of parts acetone, 5 partstriethylamine and 10 parts nonyl-phenol and the mixture was heated underreflux for six hours. After cooling, the precipitated dyestuff wasfiltered off with suction, washed with a little acetone and water, anddried. 15,4 parts of the above compound were obtained.

Agosy H )n in which X is OR, COOR, O-COR, O-

COOR, -OSO R or aryloxysulfonyl;

R is alkyl of up to 18 carbon atoms; cycloalkyl, ar-

alkyl or aryl;

R is alkyl of up to 18 carbon atoms, cycloalkyl, ar-

alkyl, aryl or C C dialkyl-amino;

' Y is halogen, alkyl of up to 12 carbon atoms or alkoxy; and n is anumber from to 3; and

B. subjecting the fiber material to a heat treatment to fix saiddyestuff on said fiber.

2. The process of claim 1 in which X is OR COOR, OCOR OCOOR, OSO R or -O-S-OR,;

R is C,-C, alkyl, cyclohexyl, methylcyclohexyl,

benzyloxy, methylbenzyloxy, phenoxy or methylphenoxy;

R is C,C akyl, cyclohexyl, methylcyclohexyl,

benzyl, methylbenzyl, phenyl, methylphenyl, ethyl- 12 phenyl,propylphenyl, chlorophenyl, methoxyphenyl, isopropoxy-phenyl orchloro-methylphenyl;

R, is C -c -alkyl, cyclohexyl, methylcyclohexyl,

benzyl, methylbenzyl, phenyl, methylphenyl, ethylphenyl, or naphthyl;

R is C -C alkyl, cyclohexyl, methylcyclohexyl,

benzyl or methylbenzyl;

R is C,-C -alkyl, cyclohexyl, methylcyclohexyl,

benzyl, methylbenzyl, phenyl, methylphenyl, ethylphenyl, propylphenyl,chlorophenyl, methoxyphenyl, or C,C.dialkylamino;

R is phenyl or phenyl substituted with alkyl of up to nine carbon atoms,alkoxy of up to 3 carbon atoms or chloro;

Y is halogen, C,-C, alkyl or C,--C alkoxy; and

n is a number from 0 to 3.

3. The process of claim 1 in which X is OR, or

4. The process of claim 1 in which X is O-COR or O-SO R,; and

n is 0.

5. The process of claim 1 in which said waterimmiscible organic solventis an aliphatic chlorohydrocarbon having a boiling point of between 40and C.

6. The process of claim 1 in which said waterimmiscible organic solventis selected from a chlorinated or a chlorofluorinated aliphatic organicsolvent having a boiling point between 40 and 150C.

7. The process of claim 1 in which said anthraquinone dyestuff issoluble in said water-immiscible organic solvent.

8. The process of claim 7 in which the dyed material is subjected to asubsequent step of (C) rinsing with water-immiscible organic solvent inwhich said anthraquinone dyestuff is soluble.

* i k i l

2. The process of claim 1 in which X is -OR2, -COOR3, -O-COR4, -OCOOR5,-OSO2R6, or -O2-S-OR7; R2 is C1-C18-alkyl, cyclohexyl, methylcyclohexyl,benzyloxy, methylbenzyloxy, phenoxy or methylphenoxy; R3 is C1-C12-akyl,cyclohexyl, methylcyclohexyl, benzyl, methylbenzyl, phenyl,methylphenyl, ethylphenyl, propylphenyl, chlorophenyl, methoxyphenyl,isopropoxy-phenyl or chloro-methyl-phenyl; R4 is C1-C16-alkyl,cyclohexyl, methylcyclohexyl, benzyl, methylbenzyl, phenyl,methylphenyl, ethylphenyl, or naphthyl; R5 is C1-C8-alkyl, cyclohexyl,methylcyclohexyl, benzyl or methylbenzyl; R6 is C1-C18-alkyl,cyclohexyl, methylcyclohexyl, benzyl, methylbenzyl, phenyl,methylphenyl, ethyl-phenyl, propylphenyl, chlorophenyl, methoxyphenyl,or C1-C4-dialkylamino; R7 is phenyl or phenyl substituted with alkyl ofup to nine carbon atoms, alkoxy of up to 3 carbon atoms or chloro; Y ishalogen, C1-C12-alkyl or C1-C6-alkoxy; and n is a number from 0 to
 3. 3.The process of claim 1 in which X is -OR, or -O-COR or -OSO2R1.
 4. Theprocess of claim 1 in which X is -O-COR or -O-SO2-R1; and n is
 0. 5. Theprocess of claim 1 in which said water-immiscible organic solvent is analiphatic chlorohydrocarbon having a boiling point of between 40* and150*C.
 6. The process of claim 1 in which said water-immiscible organicsolvent is selected from a chlorinated or a chlorofluorinated aliphaticorganic solvent having a boiling point between 40* and 150*C.
 7. Theprocess of claim 1 in which said anthraquinone dyestuff is soluble insaid water-immiscible organic solvent.
 8. The process of claim 7 inwhich the dyed material is subjected to a subsequent step of (C) rinsingwith water-immiscible organic solvent in which said anthraquinonedyestuff is soluble.